Method for refining sulphur



Patented July 18, 1944 UNITED STATES PATENT orrics METHOD ron ammo suLrnUa a corporation or No Drawing. Application October 18, 1941, Serial No. 415,638

7 Claims. (c gar- 229).

This invention relates to the refinement oi. sulphur and more particularly to the treatment of crude sulphurs for the removal of organic or carbonaceous impurities. The treatment, howshort life of the retorts brought about by the corrosive action of sulphur at the temperatures. maintained therein, and finally, due to the necessity of removing accumulations of carbonaceous residues from thechamber and the necessity for ever, is ordinarily carried out in such manner periodically discharging the complete contents that all impurities are substantially completely of the chamber to waste. It is an object of the removed, including in addition to the carbonapresent invention to provide a process of producceous impurities also inorganic matter, acid and ing refined sulphur which is economical to opmoisture. 'erateand of less danger to operators of the The invention is of primary or special value 1 equipment required. when the process is applied to the refinement of Many attempts have already ee e D relatively pure crude sulphurs, namely, those vide a substitute for the distillation process, but containing less than about 0.05 percent organic as far as applicant is aware none of these procimpurities or even less than 0.03 percent of such esses has been economically feasible. Inaccordimpurities, as are obtained, for example, by ance with these proposed processes the crude sul- Frasch minin operations. Through operation phur has been treated with various absorbent of the instant process, the carbonaceous content and decolorizing agents, such as fuller's earth, may be easily reduced to less than 0.00001 perzeolites, activated carbon, silica gel, diatomacent. For all practical purposes the product ceous earth, and the like, such treatment involvmay be described as one hundred percent rhoming, a subsequent filtration or' decantation. bic sulphur. Other proposed processes combine with the ab- A specific object of the invention is to provide sorbent treatment a treatment with chemical a process of obtaining refined sulphur of high agents, such as sulphuricacid, aluminum chloride purity from relatively pure crude sulphur at a or a combination of sulphuric acid with various st su ici ntly low t s pply the l r e d mand oxidizing agents, which treatments are followed for refined sulphur at present unsatisfied due to by washing or by filtration to remove the car-' the high cost of production. Refined sulphur iS- bonaceous impurities. Although these prior highly desirable in the manufacture of gun D W- rocesses remove a large proportion of the carr e pigments, fumigants a insectibonaceous cqntent'of the sulphur, they are not cides, and in the sterilization and preservation capable of economically produeing a refined of many agricultural products. phur of t same qualityas is produced by the According to the only process now in commerpractice of th instant invention. Ciel use for the production of fi d s ph Broadly considered, the instant invention inthe crude sulphur is distilled and the vapors convolves reacting the impurities contained in crude densed in a large masonry work chamber wheresulphur ith chloro-sulphonic acid and separatin the temperature is maintained around 100 0., the reaction products formed fr the 1- producing fiowers ofg-sulphur which condense as phun The treatment ay be carried out by a fine Powder on the walls of the chamber and/0r treating the sulphur in molten condition with a a liquid sulphur which condenses on the fioor of small quantity of the d d when the acid the chamber' 3 liquid sulphur is drawn on has reacted with the organic impurities to form into molds where it hardens in the form of blocks readily separable reaction products, removing or sticks referred to in the trade as brimstone such reaction products by any of a number of or roll sulphur. processes, including filtering or washing with The high costof production of the refined sulsuperheated t r, A steam-jacketed agitator phur in accordancewith the foregoing proc ss vessel of conventional construction may be use has caused a decrease in consumption of refined for the treatment. The intimate contact with Sulphur a Period of y s- This high 60st the acid is best eifected when the sulphur is in has been due to the large sized equipment necesa non-viscous molten form, which condition lies sary to produce a comparatively small tonnage. generally between 250 and 320 F. Furthermore, the operation of the process is dan- The reason for the high purifying power of gerous due to the extremely explosive and inchloro-sulphonic acid as compared with other flammable nature of the sulphur vapors. The agents such as fuming sulphuric acid has not process is also costly due to the deterioration and u been definitely established. The .acid appears to react with the organic impurities to form soluble sulphonates and chlorides which to some extent are polymerized and form tar-like compounds of high molecular weight.

The amount of chlorosulphonic acid used in any particular operation of the process depends upon the amount andnatureof the organic impurities in the crude sulphur treated. The only requirement is that the amount be sufilcient to convert the impurities into a separable form in a reasonable period of time. The proper amount can be readily determined by simple laboratory tests. The time of contact required for the operation depends upon several factors, including the efilciency of mixing apparatus in eifecting intimate contact between the acid and the impurities and 'the amount and nature of' the impurities. With ordinary crude sulphur and conventional agitating apparatus, a period of thirty minutes is. usually sufiicient.

In accordance with a preferred embodiment of 4 p the invention, the refinement of relatively pure but also to remove any unreacted fixed carbonaceous matter and inorganic impurities, and as well any excess or imreacted acid.

This combination treatment is preferably carried out by subjecting the crude molten sulphur to a successive treatment with the chlorosulphonic acid and the absorbent or filter aid, the acid being added and stirred into the molten sulphur for a short period, fifteen minutes usually being more than adequate, whereupon the absorbent is added and the mixture is agitated for a short period. Finally, the absorbent and A quantity of crude sulphur containing 0.020 percent organic impurities is' introduced into a steam-jacketed veuel provided with an aaltator and heated to atemperature at which the sulphur changes to a low viscosity molten condi-v tion, a temperature of 250 to 200 1";usually being sufficient. Thereupon about 0.12 of one percent of chlorosulphonic acid is added. After agitating the mixture for a period of to minutes, 0.5 of one percent of an acid activated fuller's earth are introduced and stirred into the mass for an additionalperiod of about 15 minutes. The absorbent and combined impurities are then filtered out and the pure molten sulphur passed to suitable molds such as are commonly used in the production of roll sulphur. The refined sulphur obtained is pure rhombic sulphur so free of carbonaceous impurities that its content of such matter cannot be measured by any process or apparatus heretofore known to the sulphur production art.

EXAIPLI 2 Molten sulphur is treated in the manner described in Example 1 with 0.25 of one percent of chlorosulphonic acid and then with 0.5 of one percent of ordinary fuller's earth. An extremely pure sulphur is likewise obtained by this treatment.

In order to illustrate the superiority of the present process over the most closely related processes of the prior art, a number of tests have 19 been carried out and are recorded in the tables below. In conducting the tests the various treatments were applied to an average Gulf Coast crude sulphur containing 0.025 percent carbonaceous content. The tests were conducted upon portions of the same sample of crude sulphur and under identical conditions of temperature, time of contact, filtration, and the like. The

treatment was carried out at a temperatur of about 300 F. for a total-period of thirty minutes.

20 In cases where acids and Super Filtrol are shown together, the treatments were eflected succes-' sively, the molten sulphur being agitated with the acid for 15 minutes following which the Super Filtrol was added and agitation continuedfor an additional 15 minutes. In the treatments usi the absorbents alone, the contact involved an a tation period of minutes. The Super Filtrol referred to in the table is a trade name applied to an acid treated fullers earth.

* Table I it? t' i i rod T con en 0 p N Reagent l tg oi not, roent ur a as p 1 25 iumin mso 27.4

s1? Filti ol -f 22.4 0.001

44.8 44.8 0.0(Xl75 44.8 0M4 44, 8 0. (D6 44. 8 0. 002 0 Chl osulfonic acid 5.6

Co non iullllier's earth 1;: 3 Less than 0. 00001 Les than 0.0000

Super Filtrol 11: 2 0. 0m

l P t CH re resents the empirical formula given for the car:

mu finl mltifl' found inerudo sulphur; the ratio of hydro bonaceous ororg gen to carbon was established by com analyses made on many representative samples of crude sulphur.

From the foregoing table it will be observed that the chlorosulphonic acid treatment in accordance with the present invention produces a refined sulphur of very much greater purity than is obtainable by the other processes. It will be 55 observed further that both the quantity of acid and the quantity of absorbent used in the present process are remarkably less than used'in the other processes. It may be ascertained from a. study of the table,'in particular tests Nos. 2, 6 and 7, that the sulphur trioxide content is not the controlling factor in accomplishing the purification,

for in test No. 2 the available amount is 11.2

pounds and in tests Nos. 6 and .7 it is only 4.6 pounds, per long ton of sulphur treated. '4

Since standard methods of determining the carbonaceous content of sulphur were found to be. inadequate in analyzing the refined sulphur products, a technique was developed based upon .a very sensitive color comparison. In this new method a sample of sulphur is heated to the boiling point in a suitable closed vessel and held at that temperature for a period of flveminutes, during which period the carbonaceous matter quantitatively reacts with the sulphur to produce a colored compound which after several hundred has been determined invariably..to possess the formula of approximately C4Sc.. The color of this carbon-sulphur complex is black and is so extremew finely divided and evenly distributed throughout the sulphur that, even in minute traces, it imparts a distinct discoloration to the sulphurgdepending upon' the quantity present.

In continuing the preparation oi the samples to be tested after the five minute period has elapsed, the sulphur in the vessel is permitted to.

cool and is ground and screened to separate a fraction of between 30 and 50 mesh screen. Color determination: applied to these samples indicates difierences. in composition as small as 0.00001 percent cm.

stant level in the crucible, such additions being continued until a total weight of approximately 100 grams has been added. The sulphur is permitted to burn without the application of extere nal heat until the flame goes out of its own nocord. Thereupon the crucible is dried, and the weight of the residue calculated.

The process ofthe present invention possesses many advantages over the prior art processes and In the following table the purity of the refined sulphur produced by the present invention is compared with the present commercially available refined brimstone produced by the conventional distillation process. Two different samples or the refined brimstone are compared with a sample produced in accordance with the present invention using extremely small quantitiesof' chlorosulphonlc acid and iullers earth.

These comparisons show very clearly the superiority of the present purification method.

Since a substantial proportion of refined sulphur is consumed in treatments involving buming of the sulphur, the burning quality of the refined sulphur produced by the present invention is compared below with the various prior art refined sulphurs. The burning qualities of the sulphurs, refined by the processes defined in Tables I and II, are compared in the following table.

Table III Percent free Sulphur product b Crude sulphur K10 after A101; treatment 99.0

aft: activated carbon 87. l

- liter activated lullers earth treatment 90.4

aita'sul huricacidtrea ent 96.2 lite te .0 liter chlorosulionic acid treatment 99.9-1-

refined brimstone 83.8

may be summarized as follows. The present process produces refined sulphurs having a higher purity than any products heretofore produced by the processes of th prior 'art. The present processes are applicable to the treatment of all crudes regardless ofth nature of the o ganic impurities contained therein. The equipment required to carry out the process is of relatively simple construction, and the operation or the process involves none of the problems "of explosion, fire or corrosion, or collection of the product in pow-' dered form. The cost of constructing and of operating a plant to carry out the instant process is substantially less than that required in the distillation process. For example, a plant adapted to produce '100 tons 'of refined sulphur per day using the instant process costs about one-halfthat or a retor't chamber-refinery having a capacity of only.one-tenth or one-twentieth as large. Finally. he total cost of production using the instant process is only a fraction of that of the prior processes.

It should be understood that the present invention is not limited to th specific methods of contacting and other manipulative steps and proportions disclosed herein, i'or the invention extends to all variations which will occur to those skilled in the art upon consideration of the factors involved. The scope of the present invention is limited only by the claims appended hereto.

I claim:

l. The method of obtaining sulphur substantially free from impurities from impure sulphur containing less than about .05 percent organic impurities, which comprises intimately mixing a body of said impure sulphur at a temperature of from 250320 F. with chlorosulphonic acid and with a filter aid, and separating the filter aid and the resulting reacted impurities from the sulphur.

2. The method of removing the impurities from sulphur containing less than about .05 percent organic impurities which comprises intimately mixing abody of said sulphur in molten condition with chlorosulphonic acid whereby the impurities react with the acid, and separating the reaction products from the sulphur.

3. The method of purifying sulphur containing less than about .05 percent organic impurities which comprises melting the sulphur, introducing chlorosulphonic acid into a body of the melted sulphur, agitating the resulting mixture and separating the treated sulphur from the reaction products formed with the assistance of a filter aid.

4. The method of purifying sulphur containing less than about .05 percent of organic impurities which comprises melting the sulphur, agitating tared high 'iorm crucible and igniting the contents by. means of a heated wire. As the burning progresses small portions of sulphur are contlnually added at a rate which maintains a cona body of the same. with an addition of chlorosulphonic acid whereby the acid reacts with the organic impurities, introducing into the mass a finely divided absorbent material and separating the treated sulphur from the absorbent material and impurities held therein.

5. The method of refining sulphur containing less than about-.05 percent organic impurities comprising agitating a body of impure molten sulphur in admixture with chlorosulphonic acid and tullers earth, and after the acid has reacted less than about .05 percent organic impurities comprising intimately mixing a body of the sulphur in molten condition with chlorosulphonic acid to form readily removable derivatives of organic impurities therein and separating from the body of sulphur the reacted impurities and other impurities with the aid of an addition of an acidleached earth absorbent.

7. The method of producing highly refined sulphur from ofi-colorsulphur containing less than about .05 percent organic impurities which comprises intimately contacting a body of. said 0&- color sulphur in a non-viscous molten condition with ehlorosulphonic acid and a finely divided absorbent material, and separating the treated sulphur from the absorbent and impurities held therein.

ROBERT C. HILLS.

cmwmcnm or commczuon. nte t No. 2,553,959. July 1 19%.

ROBERT c. HILIL's.

It is hereby certified that error appears hi the printed specification of the shape nunbered patent rewirl g correction as follows: Page 2, second colmn'p, Table 1, last column thereofjopposite Test No. 7, for "less than o'.oo'oo' rent-518st than o.oooo1--- endoppoelte Test No. for

'- --0. OO0" re d --G.0O02--; end that the sold Letters Patent should be read with th1s correctiohthere1n that the same may conform to the record of the casein the Patent Offtce. si ma and sealed this 29th day of August, A. D. 191m.

Leslie Fiazer (seal) Acting Commissioner-of Patents. 

